Treatment of textiles



Patented Apr. 9, 1946 or es.

I TREATWNTIOF i: 1:

David Aelony,

Dayton, @hio, assignor to Monr santo Chemical Company, a corporation of Delaware No Drawing.

Application January 29, 1942, Serial No. 428,745

9 Claims. (01. 117-1355) This invention relates to a process for treating fibrous products. It more particularly relates to a process for producing water repellent and mold resistant finishes upon textile or other fibrous products.

According to the present process I treat fibrous or textile Products with N-alkyl carbamyl or N- alkyl sulfamyl substitution products of benzoic acid. Substitution product of benzoic acid, of

the type herein contemplated may be prepared in the soluble or in the insoluble form and may be applied in either form. When applied in the soluble form the complete treatment may consist of two steps, however satisfactory application to fibrous products may also be'made employing the insoluble form and utilizing a one-step application. l

,The present invention employs compounds having the following eneral formula:

COOM

where R is a long chain aliphatic hydrocarbon residue having a carbon chain length of from 8 or an amine, the salt is generally somewhat water -soluble, however when M is a heavy metal such as Al, Cu, Zr, Fe, Zn, the salt is generally water insoluble.

- The acids of the general formula as givenabove are rather insoluble in water. They are characterized by the property of readily forming dispersions in water solution which dispersions may be produced either mechanically or by the use of dispersing agents. I have found that these dispersions may be employed to treat fibrous products for the purposeof developing waterrepellent properties. The alkali. metal, ammonium or amine salts of the acids of'the general formula as givenabove are water soluble, and aqueous solutions of such salts may likewise be employed for the purpose of.this invention. The heavy metal salts of the above acids are generally water insoluble.

Compounds of the above general formula. are

obtainable byseveral procedures. Thus, compounds of the formula:

comm

ooon

where R is a long chain aliphatic hydrocarbon to 20 carbon-atoms, X is 00 or S02, and M is a salt forming metal, hydrogen, ammonium or an f amine. When M is an alkali metal, ammonium I gradually add 200 crystalline residue having a carbon chain length of, from 8 V to 20 carbon atoms may be prepared according to the procedure described by Salzberg in U. S. Patent 2,10 23 wherein phthalic anhydride is reacted with a higher primary alkyl amine to yield an N-alkylphthalimide which is "subsequently converted by hydrolysis to the desired N alkyl phthalamic acid. 0n the other hand, compounds of the formula:

SOzNHR COOH may be prepared by treating m-chlorosulfonylbenzoio acid with a primary ing 8 or more carbon atoms.

As alkyl amines for the preparation of the N- alkyl amine containalkyl carbamyl or N-alkylsulfamyl substitution products of benzoic acid of this invention may be used octylamine, decylamine, dodecylamine, hexadecylamine, etc. I There may also be used the mixtures of the higher alkyl airlines obtained by the hydrogenation of the nitriles of commercial acid mixtures such as commercial stearic acid, commercial palm oil fatty acid, or commercial coconut oil fatty acid or the nitriles of other commercial acid mixtures such as commercial stearic acid, commercial palm oil fatty acid, or commeracid or the nitriles of other commercial acids derived from natural or syn-.

cial coconut oil fatty thetic products such as the natural oils, fats, or waxes, or acidic oxidation products of higher aliphatic hydrocarbons. The mixtures of the higher alkyl amines obtained by Hoffman degradation of the amides of such commercial fatty acids are likewise suitable as initial materials in the preparation of the various isomeric N-alkylcarbamyl or N-alkyl sulfamyl substitution products of benzoic The following example will illustrate the preparationof an N-alkylsulfamylbenzoic acid. For the preparation of 3-N-dodecylsulfamylbenzoic acid 1'. dissolve 40g. of sodium hydroxide in 200 cc. of water and add 200 g. of ice. Onto this I first pour a solution of g. of dodecylamine in 3-N-decylor 3-N-hexadecyl sulfamylbenzoic acids, the dodecylamine of the above example being substituted by octylamine, decylamine, hexadecylamine, etc., respective] a The herein described N-alkylcarbamyl or N-alkylsulfamyl substitution products of benzoic acid are especially valuable when used according to the process of this invention for application to the various textile fibers or fibrous products; namely, fabrics woven from. cotton, linen; wool,

jute, artificial fibers, yarns and the like for the purpose of producing waterproof products. These compounds may also be applied to paper forming fibers such as sulfate, sulflte and ground wood pulp, or to paper, itself. The application to such paper forming fibers is preferably done in the heater or Jordan machine wherein the herein described N-alkylcarbamyl or N-alkylsulfamyl substitution products of benzoic acid are dispersed mechanically or by the use of dispersing agents,

Since the N-alkylcarbamyl or N-alkylsulfamyl substitution products of benzoic acid herein described aresomewhat water insoluble compounds, it is preferred for the purpose of developing water repellency, to first prepare the more soluble alkali metal, ammonium or amine salts thereof. Aqueous solutions of such salts are made up, and the fabric to be treated is run through the solutions, for example, in a padding machine, dried, and then treated with a water soluble aluminum salt such as aluminum acetate or copper acetate. The N-alkylcarbamyl or N-alkylsulfamyl substition products of benzoic acid may also be used directly by preparing aqueous dispersions of them.

Although such dispersions can be prepared mechanically, their preparation is somewhat'easier if the substituted acid is dispersed in the presence of a dispersing agent. As an example of dispersing agents suitable for preparation of dispersions of the present compound may be mentioned co-.'

polymers of styrene and maleic anhydride, which copolymers have been-converted to their water soluble salts, i. e., sodium or-ammonium salts. However, any dispersing agent which is chemically stable and eifective in the presence of the N- alkylcarbamyl or N-alkylsulfamyl substitution products of benzoic acid may be used for the preparation of dispersions of the same.

This invention is illustrated but not limited by the following examples:

Example 1 I solution of a salt such as the ammonium salt of may be evaluatedas to water repellency by two tests generallyapplied by those skilled .in this art. These tests are known as the spray test and hydrostatic head test. The spray test which I employ is described in the American Dyestufls Reporter, vol. 28, page 285, for 1939. The hydrostatic head test is described in the 1940 Yearbook of' the American Association of Textile Chemists and Colorists at pages 2234. There may also be used the. hydrostatic pressure test, the spray test and the immersion test described as tentative methods in the 1941 Yearbook of the American Association of Textile Chemists and Colorists.

A sample of Indian Head cloth treated as above described showed the following degree of water- Example 2 In this example the procedure of Example 1 is followed except that instead of the 3-N-dodecylsulfamyl benzoic acid of Example 1 there is used z-N-dodecylcarbamyl benzoic acid prepared by hydrolysis of the N-dodecylphthalimide obtained upon reacting phthalic anhydride with dodecylamine. A sample of Indian Head cloth? treated with the compound and aluminum acetate according to the process described in Example 1 showed the following degrees of water-proofness. Tested with the spray test described in'the American Dyestuffs Reporter, vol. 28, page 285 for 1939 I obtained a moisture absorption of 25.7%, and a hydrostatic head value of 14.6 cm. After subjecting the treated fabric to 20 consecutive washings with soap and water. at 60 C., I obtained a spray test value of 28.0% moisture absorption and a hydrostatic head value of 12.2 cm.,

. which values indicate excellent wash resistance.

the styrene-maleic anhydride copolymer in 480 grams of water is prepared in a mechanical dispersing apparatus. A sample of Indian Head cloth is treated in the suspension contained in a padding machine, while the temperature'of the dispersionis in the neighborhood of C. The treated cloth is wrung out, air-dried or dried at temperatures of up to approximately 0., and then treated with a 5% aqueous solution of aluminum acetate either in jars for 15 minutes at 60 C. or in a padding machine for 1 to 5 ends at the same temperature. Upon allowing the treated cloth to dry at temperatures up to 100 C. and

subsequently baking it at about C.- C. for from 21:0 60 minutes,'the -treated cloth will be found to have a permanent wash resistant, water repellent property and good feel.

Fabrics treated-by the herein described process While relatively dilute solutions of the dispersions, say from 0.2% to 1% or even 4% or 5% may be employed for the application of the N-alkylcarbamyl or N-alkylsulfamyi benzoic acids to the cloth, even more concentrated dispersions, say up to 40% or 50% maybe advantageously prepared. especially with the aid of dispersing agents, and the concentrated dispersions may be diluted to a satisfactorily usable dilution prior to application to textile fabrics. In general, suitable treating solutions may contain an amount of dispersing agent ranging from 1% to 10% or more by weight of the N-alkylcarbamyl or N,-alkylsulfamy1 substitution products of benzoic acid. Such aqueous dispersions may conveniently be marketed directly as dispersions either in concentrated form or in dilute form ready for application to textiles. It is also possible to market the dry powdered N -alkyl carbamyl or N-alkylsuifamyl substitution products of benzoic acid either in the pure form or having mixed therewith any of the dispersion agents above mentioned in the dry form or the dry powdered compounds may, prior to drying. be treated with solutions of the dispersing agent and then dried to' obtain a dry powder of the N-alkylcarbamyl or N-alkylsuliamyl substitution products of benzoic acid and the dispersing agent.

If it is desired to employ an alkali metal, ammonium or amine salt of the N-alkylcarbamyl or acid for the purposes of this invention, conversion of the free acid into its salt may be effected either prior to or during the treating process;

Instead of the aluminum acetate of the above examples, any soluble aluminum salt or a heavy metal salt may be used for the purpose of this invention. Treatment of the N-alkylcarbamyl'or N-alkylsulfamyl benzoic acids impregnated fabric with a soluble aluminum salt such as alumi num sulfate, aluminum sodium sulfate or aluminum ammonium sulfate results in a permanent water repellent effect; whereas, on the other hand, treatment with the N-alkylcarbamyl of N-alkylsulfamyl benzoic acids alone, or with the soluble inorganic or organic salt of aluminum alone, does not confer permanently wash-proof water repellent properties to the fabric. Preferably I employ in my process a soluble aluminum salt of a weak acid in order to prevent attack of the fabric by a strong acid upon the decomposition of the aluminum salt. Therefore, if such a salt as aluminum sulfate is used for the process, it is advisable that immediately following its application and prior to the baking step the treated fabric is submitted to a neutralization or thorough rinsing in order to remove sulfuric acid liberated during the treatment.

Where it is desired to impart mold and rot resisting properties to fabrics, it is preferred that the after treatment with a metal salt be carried out with a copper salt. Such a copper salt as copper acetate may be employed alone or in conjunction with the aluminum salt so that either the copper salt:

or the aluminum salt:

XNHR

or mixtures of both salts ,are deposited upon the fibers.

What I claim is:

'1. The process of imparting water repellent properties to fibrous products, which comprises applying thereto a compound of the general .for-,

mula

XNHR

coon

the class:

XNHR

where R is a long chain hydrocarbon residue having from 8 to 20 carbon atoms, X is selected from-'- the group consisting of CO and so: and M is selected from the group consisting of alkali metals, hydrogen, ammonium and amines, and thereafter treating said fibrous products with a solution of a salt of a metal selected from the group consisting of Al, Cu; Zr, Fe and Zn.

3. The process of imparting water repellent properties to fibrous products, which comprises applying to said fibrous products a soluble salt of an acid of the type:

COOH

where X is selected from the class consisting of COOH where X is selected from the class consisting of CO and S02 and R is a hydrocarbon of from a to 20 carbon atoms. i

' 5. A fibrous textile product, the fibers of which are substantially coated with an insoluble salt of an acid or the formula:

OOOH

where x is selected from the class consisting of C0 and SO: and R is a hydrocarbon of from 8 to 20 carbon atoms.

6. A fibrous textile product, the fibers of which are substantially coated with an adherent insoluble salt of an acid of the formula:

SOzNHR coon where R is a hydrocarbon residue or from 8 to 20 carbon atoms.

7. A fibrous textile product, the fibers of which are substantially coated with an adherent insoluble salt of an acid 0! the formula:

CONHB COOK where R is a hydrocarbon residue of from 8 to 20 carbon atoms.

8. The product defined in claim 5, in which the insoluble salt is the aluminum salt.

9. The product defined in claim 5, in which the insoluble salt is the copper salt.

. DAVID AEIDNY. 

